CN1056867C - Polyisocyanate adhesive and sealant systems - Google Patents
Polyisocyanate adhesive and sealant systems Download PDFInfo
- Publication number
- CN1056867C CN1056867C CN92109227A CN92109227A CN1056867C CN 1056867 C CN1056867 C CN 1056867C CN 92109227 A CN92109227 A CN 92109227A CN 92109227 A CN92109227 A CN 92109227A CN 1056867 C CN1056867 C CN 1056867C
- Authority
- CN
- China
- Prior art keywords
- imino
- polymeric polyisocyanate
- substrate
- solidifying agent
- reaction system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 90
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 90
- 239000013466 adhesive and sealant Substances 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 109
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 239000000853 adhesive Substances 0.000 claims abstract description 20
- 230000001070 adhesive effect Effects 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000002023 wood Substances 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- 229920002522 Wood fibre Polymers 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 40
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 6
- 239000000565 sealant Substances 0.000 abstract description 3
- -1 enamine compound Chemical class 0.000 description 42
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 42
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 22
- 150000002466 imines Chemical class 0.000 description 20
- 239000007795 chemical reaction product Substances 0.000 description 19
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 16
- 239000012948 isocyanate Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 14
- 229910000071 diazene Inorganic materials 0.000 description 14
- 150000002513 isocyanates Chemical class 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 150000002081 enamines Chemical class 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 150000002463 imidates Chemical class 0.000 description 4
- 150000002464 imidothioesters Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical group NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 2
- SEXKDZSOKXPFFH-UHFFFAOYSA-N 1-(2-benzoylphenyl)ethanone Chemical compound CC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 SEXKDZSOKXPFFH-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LHUFCBJNLRGIEV-UHFFFAOYSA-N C(C)(=O)C1=C(C(=O)C2=CC=CC=C2)C=CC=C1.N1CCNCC1 Chemical compound C(C)(=O)C1=C(C(=O)C2=CC=CC=C2)C=CC=C1.N1CCNCC1 LHUFCBJNLRGIEV-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 235000014466 Douglas bleu Nutrition 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 240000001416 Pseudotsuga menziesii Species 0.000 description 2
- 235000005386 Pseudotsuga menziesii var menziesii Nutrition 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000011093 chipboard Substances 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011094 fiberboard Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000010107 reaction injection moulding Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- OVUBWTFSSKMBOO-UHFFFAOYSA-N 1-phenylethanone piperazine Chemical compound C(C)(=O)C1=CC=CC=C1.N1CCNCC1 OVUBWTFSSKMBOO-UHFFFAOYSA-N 0.000 description 1
- XPZBNIUWMDJFPW-UHFFFAOYSA-N 2,2,3-trimethylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1(C)C XPZBNIUWMDJFPW-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- KYQHMTLLFIFUAN-UHFFFAOYSA-N C(C(C)O)O.[O] Chemical compound C(C(C)O)O.[O] KYQHMTLLFIFUAN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940125718 cold curing agent Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011101 paper laminate Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- LXUQDZITPQYMIR-UHFFFAOYSA-N thiourea;urea Chemical compound NC(N)=O.NC(N)=S LXUQDZITPQYMIR-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8038—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3225
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8041—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3271
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Sealing Material Composition (AREA)
Abstract
Improved sealants and adhesives derived from polyisocyanates having aromatically linked -NCO groups are cured at ambient temperatures when combined with a curing agent comprising an imino- and enamino-functional compound. These two component resin systems may be employed in fabricating multi-substrate laminates, especially those comprising lignocellulosic and cellulosic materials, such as wood and paper.
Description
The present invention relates to aromatic polyisocyanate reaction system, it is particularly effective as tackiness agent and seal gum.The invention particularly relates to the reaction system of two kinds of components, comprise that aromatic polyisocyanate is used as tackiness agent and isocyanate activity compound is used as solidifying agent.The invention still further relates to laminating material and/or the sealing material of using two kinds of new component systems.
Various different resins are used for the processing of laminated woody and papery structure always, and for example laminated thin plank (LVL) comprises glued board, chipboard, sawdust-board and paper tube.At the tackiness agent of selecting to be used for processing described goods, an important consideration is to promote to solidify required solidification rate and temperature.As a rule, treat that the adherent sotck thinkness surpasses 3 centimetres, like this, penetration of heat is very slowly, need expend considerable time and energy.
In fact, the most widely used tackiness agent is Resorcinol/phenol-formaldehyde type resin, and it can provide fabulous tackiness, but still needs thermal activation and persistent set time.Another shortcoming that in use runs into is that it presents black, so that the finished product lack magnetism aesthetically.Using a shortcoming again of aerodux is that they can not use with containing the high-moisture substrate effectively.In view of the wooden substrate of majority all contains 10% (weight) or more moisture, therefore must carry out drying treatment, so that their contained humidities are about 5% (weight) to these substrates.When handling, then cause the expense and the time that reduce and increased application resol production woodwork of wooden volume for the moisture that reduces wooden substrate.
Isocyanate-crosslinked latex also ripple is used as tackiness agent.But even heating, its solidification rate is still quite low.In the forming process of thin plate, fiberboard and paper laminate, polymeric polyisocyanate is used as the tackiness agent of making cellulose materials, this class purposes for polymeric polyisocyanate requires solidification value to reach 200 ℃ or higher usually, so that obtain acceptable actual cohesive strength.
In the known prior art, in injection molding reaction system, use polymeric polyisocyanate and imino-and enamino functional compound.For example, United States Patent (USP) has been introduced a kind of reaction system of making polymkeric substance by the reaction injection molding(RIM) method for No. 4794129, this system is made up of a kind of organic aromatic polyisocyanate and a kind of isocyanate response composite, and described composition comprises at least a imino-functional compound.United States Patent (USP) has disclosed a kind of reaction injection molding(RIM) system for No. 4935460, wherein the A component is a kind of organic polymeric polyisocyanate, the B component is a kind of isocyanate-reactive components, and it comprises the reaction product that isocyanate-terminated polyurethane(s) gives polymers and imino-functional compound or contains enamine compound.Yet, also do not have one piece of patent to disclose its reaction system and can be used as tackiness agent or seal gum.
United States Patent (USP) is also introduced for No. 3865791 with comprising that monoene amine and polymeric polyisocyanate partial confounding compound prepare the method for giving polymers, and this then polymers that gives can combine also moisture-curable with more polymeric polyisocyanate.United States Patent (USP) 4853454 has been introduced a kind of single component moisture-curable polyurethane(s) system, and it comprises that polyurethane(s) gives polymers and Polyaldimines.The composition that these patents are introduced can be used as coating, casting material, repair material and joint cement.But these patents are not disclosed in the preparation composite product (for example sawdust-board) as yet, these compositions and wood fibre or cellulose materials bonded purposes.
People need a kind of cold-set resin system, and it can fully solidify in room temperature with in short duration, but also should have the working life that is enough to be suitable for scale production.In theory, this tackiness agent system can at room temperature solidify in 30 minutes, and its operation surpasses 5 minutes working life, and the bond strength that is provided is equal to or greater than existing resin system.
Another need be tackiness agent can with contain the high-moisture substrate, use together as wood fibre or cellulosic substrate especially.
Therefore, but one of purpose of the present invention provides a kind of tackiness agent of cold-curing/seal gum reaction system.
Two of purpose of the present invention provide a kind of can room temperature or near under the room temperature than short duration in solidified tackiness agent/seal gum reaction system.
Three of purpose of the present invention provides a kind ofly operates working life greater than 5 minutes tackiness agent/seal gum reaction system.
Four of purpose of the present invention provides the tackiness agent system that a kind of bond strength is equal to or greater than existing resin system.
Five of purpose of the present invention provide a kind of can with the substrate that contains than high-moisture, for example tackiness agent that uses together of wood fibre or cellulosic substrate.
Above-mentioned purpose and other purposes all can reach by reaction system of the present invention.
The present invention relates to a kind of low-temperature setting adhesive or seal gum reaction system, it is applicable to the preparation of wood fibre and cellulose composite, also relate to the method for this reaction system with wood fibre or mutual sealing-in of cellulosic substrate or adhesion, described liquid adhesive/seal gum reaction system comprises:
(a) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0.
(b) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
The method for preparing wood fibre or cellulosic substrate mixture comprises the steps:
(a) react the surface that system applies one of described substrate with liquid adhesive, described reaction system comprises:
(i) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0.
(ii) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
(b) compressed together these substrates;
(c) solidify this adhesive reaction system.
The invention still further relates to a kind of reaction system, it comprises
(a) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0.Wherein, polymeric polyisocyanate is not to give polymeric isocyanate;
(b) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
The invention still further relates to the method that described substrate is bonded together, this method comprises the steps:
(a) react the surface that system applies one of described substrate with liquid adhesive, the system of described reaction comprises:
(i) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.4 to 4.0.Wherein, polymeric polyisocyanate is not to give polymeric isocyanate;
(ii) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
(b) compressed together these substrates;
(c) solidify this adhesive reaction system.
The method that seals substrate surface according to the present invention comprises the steps:
(a) be applied to few substrate surface with liquid sealant reaction system, described reaction system comprises:
(i) polymeric polyisocyanate, isocyanate groups and number average isocyanate functionality that it has the aromatics connection are 1.8 to 4.0, wherein, polymeric polyisocyanate is not to give polymeric isocyanate;
(ii) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
(b) solidify seal gum reaction system.
Being used for organic polymeric polyisocyanate of the present invention, to have the number averaged isocyanate functionality be 1.8 to 4.0, is good with 2 to 3; Number-average molecular weight is 100 to 5000, and with 120 to 1800 for well, the best is 170 to 800.In comprising the described class of polyisocyanate salt, the isocyanate groups of molecular fraction at least 50 (the best at least 90) is directly connected in aromatic ring.
Suitable aromatic polyisocyanate comprises for example to phenylene diisocyanate; Between phenylene diisocyanate; 2,4 toluene diisocyanate; 2, the 6-tolylene diisocyanate; Naphthalene diisocyanate; The dianisidine vulcabond; Polymethylene biphenyl polymeric polyisocyanate; 2,4 '-'-diphenylmethane diisocyanate (2,4 '-MDI); 4,4 '-'-diphenylmethane diisocyanate (4,4 '-MDI); 3,3 '-dimethyl-4,4 '-two penylene vulcabond; Functionality is greater than 2 polyethylene diphenylmethane polymeric polyisocyanate; And composition thereof etc.The MDI isomer (2,4 ' and 4,4 '), the mixture of these isomer and polyethylene diphenylmethane polymeric polyisocyanate, polyphenylene methane polymeric polyisocyanate and derivative thereof is preferably.Polyphenylene methane polymeric polyisocyanate and derivative thereof are best.
Polymeric polyisocyanate can comprise a small amount of aliphatic polymeric isocyanate.Suitable aliphatic polymeric isocyanate comprises isophorone diisocyanate; 1, the 6-HDI; 1,4-cyclohexyl diisocyanate; The saturated analogues of above-mentioned aromatic polyisocyanate; And composition thereof etc.
Can use suitable uretonimine modified polyisocyanate, usually with following method preparation: in the presence of carbodiimide compound, aromatic polyisocyanate is heated to temperature of fusion above polymeric polyisocyanate, for example 140 ℃, make the part isocyanate groups be converted into carbodiimide, make the reaction of carbodiimide groups and unreacted isocyanate groups then, generate the uretonimine group.
Can use suitable isocyanate-terminated prepolymer, and prepare:, comprise aminated polyvalent alcohol or its imines/enamine reaction excessive polymeric polyisocyanate and polyvalent alcohol by following method.Term used herein " isocyanate-terminated prepolymer " comprises prepolymer and false prepolymer, that is, the mixture of prepolymer and polymeric polyisocyanate prepares prepolymer thus.The polyvalent alcohol of suitable preparation prepolymer comprises:
(a) molecular weight is 60 to 400, the average hydroxy functionality is 1.9 to 4 polyether glycol and/or hydrocarbyl polyol;
(b) molecular weight is at least 400, the best be 1000 or higher, average hydroxy functionality be 1.9 to 4 polyethers (and/or thioether) polyvalent alcohol;
(c) molecular weight is 100 to 1000, the average hydroxy functionality is 1.9 to 4 polyester polyol.
According to the present invention, isocyanate-terminated prepolymer is used to prepare wood fibre and cellulose composition is effective equally.Particularly preferred isocyanate-terminated prepolymer is the reaction product of excess polymeric MDI and polyether glycol, and wherein to have number-average molecular weight be 400 to 2500 to polyvalent alcohol.The end capped prepolymer of this kind isocyanate generally should have free NCO content greater than 10%, is preferably greater than approximately 16%, and the best is about 16～24%.Being used for the polymeric MDI composition that the present invention suits is Rubinate M, can be available from American I CI.
The solidifying agent of described tackiness agent/seal gum reaction system is the isocyanate-reactive composition with at least 1 imino-functional linkage or enamino functional linkage.These " functional linkage " refer to imino-and/or the enamino that is present in the curing agent composition.Described solidifying agent can contain 1 or more other isocyanate reacting group, especially hydroxyl or carboxylic acid group arbitrarily.
" reaction system " described herein refers to the system or the system of reactive component, in this system, and each component unreacted or complete reaction not, but in use interact.
" imino-is functional " as herein described refers to reactant and contains following radicals:
In the formula: X, Y and Z are chemical parts, their common rest parts that forms described compound, and be selected from hydrogen and organic group independently of one another, these groups are connected in the imino-unit of described compound: C=N-by N, C, O, S, Si or P, the unitary central carbon atom of described imino-is connected on 3 atoms; But, if its prerequisite is X and Y all is organic groups, and X or Y be connected in the imino-unit by N, then, all the other groups (X or Y) preferably are not connected in the imino-unit by C or N, but are connected in the imino-unit by O, S, Si or P (preferably by O or s).Therefore, some amidine and guanidine preferably can solidifying agent as imino-official of the present invention.In addition, in said structure, unitary carbon atom of imino-and nitrogen-atoms should not be combined in all that aromatic ring or other are intact to be amounted to yoke ring or even can be connected to form together within the ring system of ring by X, Y and Z.It is desirable to Z and be connected in the imino-unit by carbon atom, X is H or the organic group that is connected by C, N or O separately with Y.It would be desirable by aromatic carbon atom and connect X, Y and Z.
Multiple imino-functional compound and enamino functional compound all are suitable for and make solidifying agent of the present invention.In general, solidifying agent can be selected from single imines, imidoether, imino-thioesters, isourea, isothiourea and enamine.
Suitable imino-functional compound comprises the compound of listing in following Table A, but not limited thereto.Table A
Single imines
Imido-ester
Imido-ester (aromatics)
The imido thioesters
Imido thioesters (aromatics)
Single imines
Single imines (aromatics)
Imido-ester (aliphatic series)
Imido-ester (aromatics)
Imido thioesters (aliphatic series)
Imido thioesters (aromatics)
Isourea
Isourea
Isothiourea.
Isothiourea. in the formula: R and Ar are respectively divalent aliphatic and the organic linking group of aromatics;
Expression H or organic group, for example polyethers or hydrocarbon chain or hydrocarbyl group as shown in Table, are connected in described imino-(C=N) functional group,
Can be simple function or polyfunctional;
R
6Be the organic aliphatic group of H or monovalence, contain 1 to 10 carbon atom;
R
7And R
8It is the organic aliphatic group of monovalence; Contain 1 to 10 carbon atom;
Ar ' is the organic aromatic group of monovalence, contains 4 to 18 carbon atoms.
R
5, R
6, R
7, R
8, Ar and Ar ' expression group be that the professional is known, specifically, R for example
5Can be propylidene, Ar can be methoxy penylene, R
6Can be propyl group, R
7Can be propyl group, R
5Can be propyl group and Ar ' can be methoxyphenyl.
The example of other suitable imino-official energy solidifying agent can comprise:
X represents O or S, R in the formula
1, R
2And R
3Expression by aliphatic carbon atom in shown in the organic group of structure, Ar and Ar
1The organic group of structure shown in expression is connected in by aromatic carbon atom.These groups can be identical also can be different.Arbitrary group all can contain heteroatoms, and they can connect together and form ring (being confined in the basic definition of above-mentioned " imino-official energy ")
More than various in preferably in the formula one or more substituting groups comprise other isocyanate-reactive (or potential) functional group.These additional functionality preferentially are selected from imino-/enamino functional group class, hydroxyl (or thiol) class; And/or carboxyl class.It is polyfunctional it is desirable to these solidifying agent, with two and many imines be the best.
Above-mentioned various in, be connected in the 5 or 6 joint rings that imino-unitary any 2 or a plurality of substituting group can be combined into non-aromatics.This ring can be carbocyclic ring or heterocycle, this depend on bonded specified substituent for example and combined be unitary carbon atom of imino-or nitrogen-atoms (or both all are).
When aromatic group is present in the imino-unit, link on the described unitary carbon atom to well with them, best is, and described aromatic group has not charged or give electron substituent group, for example H, alkyl, alkoxyl group, N, groups such as N-dialkyl-7-amino.
Aromatics imino-functional compound, those compounds that refer in particular at least 1 aromatic ring are directly made up on the C=N unit that is connected in aromatics imino-functional molecule, and they are preferred solidifying agent.Best solidifying agent is the aromatics imino-functional compound that per molecule contains 2 or more active function groups.Preferred adhesive/seal gum reaction system comprises polyphenylene methane isocyanic ester and aromatics imino-functional compound.Another preferred adhesive/seal gum comprises aromatics imino-functional compound and isocyanate-terminated prepolymer, this prepolymer is that the diphenylmethanediisocyanate and the polyether glycol, particularly number-average molecular weight of excess polymeric is the reaction product of the polyether glycol of 400 grams 2500.
The specific examples of preferred imino-functional compound comprises monoester family and/or aromatic aldimines and/or ketoimine, and is as follows:
Dytek-A MI BK diimine
Dytek-A MI BK pimelinketone diimine
Thanomin IMBK imines
Hexamethylene diamine MI BK diimine
Diethylenetriamine MI BK diimine enamine
N-(2-amino-ethyl) piperazine ring hexanone imino-enamine
Dytek-A furfural diimine
Thanomin benzaldehyde imines
2-(2-amino-ethyl)-thanomin furfural imines
The poly-imines (and ring position isomer, wherein n=0 to 15) of poly-aminophenyl-methane MI BK
Poly-aminophenyl-methane furfural poly-imines, wherein n=0 to 15
1-eight decyl amine benzaldehyde imines
Tallow diamine furfural diimine
Be used for best imino-functional compound of the present invention at present and comprise the product that produces by following reaction, that is: benzaldehyde and 2-methyl isophthalic acid, the 5-pentane diamine is reacted; Furfural and 2-methyl isophthalic acid, 5-methane diamine reactant and diamino-ditan (pure type or aggretion type) and benzaldehyde or furfural reaction.In case of necessity, available ketone, for example mibk (MI BK) or pimelinketone replace aldehyde.
Dytek-A MI BK diimine can be by following method preparation, that is, Dytek-A is the 2-methyl isophthalic acid, and 5-pentane diamine (also can be described as 2-methylpent methylene diamines) (can be available from E.I.duPont de Nemours ﹠amp; Co.) with mibk (MEBK) reaction.Dytek-A cyclohexanone diimine can be made by Dytek-A and pimelinketone reaction.Dytek-A furfural diimine can make by Dytek-A and furfural reaction.Usually, these compounds can promptly, place narrow-necked bottle with 1 mole of Dytek-A by following method preparation, add 2.3 moles of MI BK pimelinketone or furfural then lentamente, mixed with it.Before adding MI BK, pimelinketone or furfural, Dytek-A also can mix with dry toluene.General available 0.5 to 1.0 mole toluene.During adding Dytek-A, initial reaction temperature is controlled at about 85 ℃, heats up then, and reactant refluxes a few hours, and the best is about 2 hours.
The compound that enamine compound comprises following structure that contains that can be used as solidifying agent of the present invention:
With
A, B, D, E, G, J and L represent hydrogen or the organic group that replaces arbitrarily separately respectively in the formula, and arbitrary A, B, D and/or arbitrary E, G, J, L all can link together arbitrarily, form one or more carbocyclic rings or heterocycle.
In the preferred enamino functional compound of majority, E, G, J and L are not hydrogen.Especially effectively the enamino functional compound contains 2 or more a plurality of functional group, and this is because arbitrary A, B, D, E, G, J and/or L are the groups of the one or more addition of termination functional group.Imino-and/or alkene ammonia are best " addition " functional groups.
Preferred enamino functional compound comprises that the imines/enamine functionality of compound is those compounds of 2 to 4.
Suitable enamino functional compound can adopt currently known methods to make, and, contains the carbonyl compound and the secondary amine reaction of at least 1 α-hydrogen atom that is.Described carbonyl compound, for example aliphatic series, cyclic aliphatic or araliphatic aldehydes or ketones, specific examples is acetaldehyde, propionic aldehyde, isobutyric aldehyde, hexanal, hexamethylene aldehyde, acetone, methyl. ethyl ketone, benzyl, methyl ketone, cyclopentanone, pimelinketone, trimethylcyclohexanone, methyl phenyl ketone, and composition thereof etc.Described secondary amine, for example secondary amino group functional compound.
The example that preferably contains enamine compound comprises as follows:
Piperazine MEK two enamines
Diethanolamine pimelinketone enamine
N-(2-hydroxyethyl) piperazine ring hexanone enamine
Piperazine-methyl phenyl ketone two enamines
The methyl phenyl ketone enamino diamines of diethylenetriamine
Can prepare suitable imino-functional compound and the enamino functional compound of doing the cold-curing agent by existing synthetic technology.For example, according to the technology that United States Patent (USP) is introduced for No. 4794129, No. 4906674, No. 4910279, No. 4935460 and No. 4952660, all can prepare the imino-official can solidifying agent and enamino official energy solidifying agent.Described patent is all classified the reference of this paper as.Some suitable imino-functional compound and enamino functional compound is the commercial goods, for example! The azoles quinoline is commercially available liquid product, and its structural formula is as follows:
R is-CH in the formula
3Or-CH
2CH
3Suitable imino-functional compound and enamino functional compound can prepare respectively, or under the possibility situation, when the tackiness agent preparation, preparation (that is to say on the spot, for example in the presence of interior dewatering agent or absorbent filler, suitable amine is mixed with suitable aldehyde and/or ketone, add isocyanate component then).
It is 57 to 10000 that suitable isocyanate-reactive solidifying agent generally has number-average molecular weight, preferred 80 to 7000, and the best is 100 to 1000.
The solidifying agent of above-mentioned most polymeric polyisocyanate and isocyanate-reactive solidifying agent and other similar structures is a low-viscosity (mobile) liquid, and mobile and low viscosity makes and is easy to be fit to tackiness agent/seal gum reaction system.In addition, when the application tackiness agent/when seal gum reacted system, the low-viscosity (mobile) liquid solidifying agent can play flow ability modifying agent.Therefore, natural, polymeric polyisocyanate and solidifying agent at room temperature all are in a liquid state.Yet one of each component of this system (being polymeric polyisocyanate or solidifying agent) is for solid is possible, as long as before tackiness agent/seal gum reaction system is applied to substrate, this component can be dissolved in other liquid ingredient fully.This will guarantee to be in a liquid state when being applied to substrate when tackiness agent/seal gum reaction system.
Also polymeric polyisocyanate and curing agent component can be applied to substrate, rather than before being applied to substrate, they be mixed.When using respectively,, promptly on this substrate, form tackiness agent/seal gum reaction system in case second component is applied to substrate.When each component was used respectively, they should all be in a liquid state.Yet, preferably before the reaction system is applied to substrate, polymeric polyisocyanate and solidifying agent are mixed preparation fluid binder/seal gum reaction system.
Polymeric polyisocyanate and solidifying agent can mix by any suitable device.Because they are low-viscosity (mobile) liquid usually, be easy to by mixing together.When polymeric polyisocyanate and solidifying agent are applied to substrate (conventional filler is as lime carbonate) when mixing before, can use thinner, for example propylene carbonate.Should be appreciated that the polymeric polyisocyanate in the reaction system can comprise one or more polymeric polyisocyanates, and in the reaction system, can use one or more imino-s or enamino official energy solidifying agent.
The isocyanate groups that polymeric polyisocyanate and solidifying agent chemical combination make aromatic polyisocyanate to the solid molecule number of the isocyanate-functional of solidifying agent than at least about 2: 1 for good, isocyanate groups is preferably about 3: 1 to 10: 1 to the molecule number ratio of imino-or enamino functional linkage.
If polymeric polyisocyanate and solidifying agent mixed before being applied to substrate, the system that obtains has at least 5 minutes operation working life, and operation working life of most tackiness agents/seal gum system was considerably beyond 5 minutes.For example, the operation of tackiness agent of the present invention/seal gum system reaches a couple of days, a few weeks longer even some months working life.
Imino-used herein and enamino official can be ideal much than amine or polyvalent alcohol solidifying agent by solidifying agent.Usually amine and polymeric polyisocyanate reaction.Solidifying agent of the present invention begins when mixing with aromatic isocyanate that reaction is not rapid, and conventional amine and polymeric polyisocyanate react rapidly, so system of the present invention can have than the working life of growing during with the effectization agent than conventional amine.When using solidifying agent of the present invention, appear inductive phase, and during this period, the reaction that generates polymkeric substance does not take place, and is perhaps extremely slow.This inductive phase is usually succeeded by fast setting reaction, has system than long pot life though the polyvalent alcohol solidifying agent can provide than containing the polyamine system, and polyvalent alcohol needs catalyzer, and when it and polymeric polyisocyanate react, can produce undesirable foaming.In general, tackiness agent of the present invention/seal gum reaction system foams with denier, perhaps not foaming.
Used solidifying agent of the present invention and aromatic isocyanate reaction can be regarded direct reaction as, general no volatile matter or monomer by product in reaction.Yet the character of the process of reaction may change with the different of substrate type with solidifying agent.In addition, when this tackiness agent/seal gum is applied to substrate, there are active hydrogen form or organic or metal ion on it, then can quicken to solidify.
Liquid adhesive of the present invention/seal gum reaction system can be used on the various substrates, also can be used on the different sorts substrate together bonded to each other.For example, this system can be used for wood and cement as sealing ply, perhaps can be used for metal substrates is adhered on the wooden substrate.When this system is used as sealing ply, it is used for substrate, can improve the character and the water resisting property of substrate.When two kinds of substrates are bonded together, preferably, at least a substrate material is selected from wood, paper, rice husk, cement, stone, cotton, grass, bract, bagasse, nutshell, polymeric film and polymer flake, polymer foams, metal and filamentary material.This system can be used for making many substrate component or laminate, especially those comprise xylogen or cellulose materials, the goods of wood or paper for example, as glued board, laminated web, thin plate, sawdust-board, fiberboard, chipboard and directed woodwork, for example available from " Parallam " of ICI Americals, Inc.
The ideal substrate is to contain the moisture substrate.Usually, substrate to contain moisture low more, tackiness agent/seal gum system is long more set time, moisture 10 to 20% (weight) that are divided into of preferred substrate are the best with 12 to 15% (weight).
Though tackiness agent of the present invention/seal gum system is the cold-curing composition, that is, they can solidify to room temperature at about 0 ℃, also can thermofixation.Therefore, this system can solidify in about 0 ℃ to 250 ℃ scope usually, preferably in about 23 ℃ (room temperatures) to 125 ℃ of curing, be the best with 23 ℃ to 110 ℃.Generally, these system great majority at room temperature can fully solidify in 30 to 60 minutes.
When this system was used for two kinds of substrates are adhered to each other, the surface of one of described substrate was coated with usually with this system, and the surface of coated is again facing to the surface compacting of second substrate.Available ordinary method is for example sprayed, method such as brushing, applies these surfaces with this system.The second substrate matter surface facing to compacting first substrate is not coated with usually with this system.Yet, before described two substrates force together, also that surface can be coated with this system.After these substrates forced together, they are retained to this system under pressure fully solidified, so that bonds together securely mutually between the surface.Usually, to maintain 1.0 to 200psi be enough to pressure.
Describe the present invention in detail by following embodiment, but do not limit the scope of the invention.Embodiment 1
Prepare '-diphenylmethane diisocyanate (MDI) prepolymer by following method, promptly, get 55.60 parts of MF182 (available from the '-diphenylmethane diisocyanate mixture of ICI Americals, Inc) and 44.07 parts of Niax PPG2025 (molecular weight available from Union Carbide company is 2025 total oxygen propylene glycol) reaction, after reactant mixes, under about 75 ℃, stir and heated several hours, generate viscosity 3000CPS, the MDI prepolymer of free NCO content 16%, after this prepolymer is cooled to room temperature, add 0.26 part of Niax A-4, B-(dimethylamino) N, the amine catalyst of N-dimethyl propylene acid amides (available from Union Carbide company) is as described tackiness agent/polymeric polyisocyanate of seal gum reaction system and the catalysts between the solidifying agent.
After Niax A-4 adds prepolymer, mibk (MI BK) imines that mixes 64.5 parts of prepolymers, 6.5 parts of propylene carbonates (thinner), 25.8 parts of lime carbonate (filler) and 3.2 parts of Dytek A in narrow-necked bottle is with preparation tackiness agent/seal gum system.The MI BK imines of Dytek A prepares by following method,, restrains Dytek A (available from E.I.duPont de Nemours ﹠amp with 116.2 that is; Co.. 2-methyl pentamethylene diamine) be added in the narrow-necked bottle that contains 65 gram dry toluenes, after Dytek A and toluene mix, under agitation, slowly splashed into 230.37 gram MI BK from dropping funnel in 30 minutes, initial reaction temperature is controlled at about 85 ℃.After about 30 minutes, can heat up, gained moisture is collected in the Dean and Stark apparatus.Continue to reflux 2 hours, when outlet temperature reaches 150 ℃ of left and right sides, no longer produce moisture, show, do not had unreacted amine and existed with infrared analysis.
About 6 minutes of the working life of described tackiness agent/seal gum system, this system is with 111 gram/rice
2Consumption be applied to a side of plank,,, under the pressure about 200psi, each plate pressed stick together facing to the surface that is not coated with compound plate by a side of coated.When tackiness agent/seal gum system is at room temperature consolidated after 30 minutes removal pressure.Products obtained therefrom is easy to processing, and has fabulous internal bond strength.
Tackiness agent/the coating of seal gum system also can be used as the seal gum on plate surface.This coating can at room temperature be solidified about 1 hour.Described plate demonstrates fabulous water resisting property.Embodiment 2
Except replacing repeating embodiment 1 outside the imines (the MI BK imines of DytekA) as solidifying agent with conventional polyvalent alcohol, quadrol (according to propylene oxide, the ethylene diamine that the hydroxyl-functional cross-link bond extends has hydroxyl value 770, available from Mobay and BASF).The amount of each component of tackiness agent/seal gum system is as described below: the MDI prepolymer of 64.1 parts of embodiment 1,6.5 parts of propylene carbonates, 25.6 parts of lime carbonate and 3.2 parts of quadrols.Be 5 minutes the working life of this tackiness agent/seal gum, and the shearing resistance of this product is lower than the product of embodiment 1.Employing boils-shearing resistance of drying-boiling test method test products, this test comprises: get 2.5 centimetres of samples of 7.6 cm x and place water to boil 4 hours, this sample was put into 60 ℃ of baking oven inner dryings 16 hours, again it is placed water to boil 4 hours, put into the cold water chilling, specimen is immediately determined its shearing resistance then.Delamination during boiling appears in the quadrol sample, and the pressure of the about 160psi of product needed of embodiment 1 could be separated the plate that is adhered to one another.Embodiment 3
The adhesive reaction system prepares by following method, that is, 40.0 parts of lime carbonate of MDI prepolymer and 10 parts of propylene carbonates and 5.0 parts of Dytek A furfural diimines of getting 100 parts of embodiment 1 mix.Dytek A furfural diimine prepares by following method,, restrains DytekA (available from E.I.du pont de Nemours ﹠amp with 116.2 that is; Co. 2-methyl pentamethylene diamine) be added in the narrow-necked bottle, under agitation slowly splashed into 193.14 gram furfural diimines from dropping funnel in 30 minutes then, initial reaction temperature is controlled at about 85 ℃.After about 30 minutes, can heat up, gained moisture is collected in the Dean and Stark apparatus.Continue to reflux 2 hours, when outlet temperature reaches 150 ℃ of left and right sides, no longer produce moisture, infrared analysis shows not had unreacted amine and existed.Products obtained therefrom is a dark-brown liquid.
Be a couple of days the working life of described tackiness agent system, and this system is with 156 gram/rice
2Consumption be applied to the 3 layer Douglas fir thin plate of water content greater than 10% (weight), it is alternate stacked that these three layers of thin plates are pressed grain direction, under room temperature, 200psi pressure, solidified 30 minutes then, gained glued board product has fabulous internal bond strength, fabulous water resisting property, and is suitable for outdoor application.Embodiment 4
Tackiness agent/seal gum system prepares by following method, promptly, 100.0 parts of Rubinate M (available from the polymkeric substance MDI of ICI Americals, Inc), 20.0 parts of lime carbonate and 25.0 parts of aromatic imines are mixed, and aromatic imine is the reaction product of MI BK and 4,4 '-diaminodiphenylmethane.The preparation of aromatic imine, that is, and with 115.65 grams 4,4 '-diaminodiphenylmethane be added to contain 50 the gram dry toluenes and 0.25 the gram tosic acid narrow-necked bottle in, then under agitation, slowly splashed into 134.35 gram MI BK from dropping funnel in 30 minutes, initial reaction temperature is controlled at about 85 ℃.After about 30 minutes, can heat up, gained moisture is collected in the Dean and Stark apparatus.Continue to reflux 2 hours, when outlet temperature reaches 150 ℃ of left and right sides, no longer produce moisture, infrared analysis shows not had unreacted amine and existed.The finished product are light brown liquid.
Be a couple of days the working life of described tackiness agent system, and this system is with 156 gram/rice
2Consumption be applied to the 3 layer Douglas fir thin plate of water content greater than 10% (weight), it is alternate stacked that these three layers of thin plates are pressed grain direction, hot-press solidifying 3 minutes under 149 ℃, 200psi pressure then, gained glued board product has fabulous internal bond strength, fabulous water resisting property, and is suitable for outdoor application.
These embodiment prove that reaction system of the present invention can be used as tackiness agent and seal gum, make products obtained therefrom have fabulous internal bond strength and fabulous water resisting property.These embodiment prove that also employed solidifying agent surpasses conventional polyvalent alcohol, described solidifying agent and polyisocyanate reactant salt, this tackiness agent/seal gum react system can with contain the high-moisture substrate, for example wood fibre or cellulosic substrate are used together.Described embodiment proves that also this reaction system can cold-curing or thermofixation, and when aromatic imine was used as solidifying agent, this system can prolong working life.
Do not deviating under the spirit one-tenth essential characteristic of the present invention, the present invention can summarize other specific forms.
As benchmark, represented protection scope of the present invention with claims.
The demonstration form of the embodiment of the invention comprises:
A kind of liquid adhesive/seal gum reaction system that is applicable to wood fibre and cellulose composite preparation, it comprises:
(a) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0;
(b) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
A kind of liquid adhesive/seal gum reaction system that is applicable to wood fibre and cellulose composite preparation, it comprises:
(a) polymeric polyisocyanate, it have isocyanate groups that aromatics connects and number averaged isocyanate functionality be 1.8 to 4.0 and number-average molecular weight be 100 to 5000;
(b) liquid curing-agent, it has at least one imino-or enamino functional linkage, and wherein, the number-average molecular weight of solidifying agent is 57 to 10000; The isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
Polymeric polyisocyanate and solidifying agent at room temperature are that polymeric polyisocyanate has the number average molecule and is changed to 100-5000 in this class reaction system of liquid, and it is 120 to 1800 that polymeric polyisocyanate has number-average molecular weight; It is 170 to 800 that polymeric polyisocyanate has number-average molecular weight; Isocyanate is 3: 1 to 10: 1 with the ratio of imino-or enamino functional linkage; It is 2 to 3 that polymeric polyisocyanate has the number averaged isocyanate functionality; Wherein polymeric polyisocyanate is isocyanate-terminated prepolymer; Prepolymer is the reaction product of excess polymeric '-diphenylmethane diisocyanate and polyether glycol; It is 400 to 2500 that polyvalent alcohol has number-average molecular weight; Solidifying agent is an aromatics imino-functional compound, wherein, has at least 1 aromatic ring to be directly connected to the C=N unit of aromatics imino-functional molecule; Aromatics imino-functional compound per molecule contains 2 or more; Polymeric polyisocyanate is a polyphenylene methane polymeric polyisocyanate, and solidifying agent is an aromatics imino-functional compound; Polymeric polyisocyanate is isocyanate-terminated prepolymer, and prepolymer is the reaction product of excess polymeric '-diphenylmethane diisocyanate and polyether glycol, and solidifying agent is an aromatics imino-functional compound; It is 400 to 2500 that polyvalent alcohol has number-average molecular weight; It is 57 to 10000 that solidifying agent has number-average molecular weight; It is 80 to 7000 that solidifying agent has number-average molecular weight, and it is 100 to 1000 that solidifying agent has number-average molecular weight; Solidifying agent is selected from single imines, imidoether, imino-thioesters, isourea, isothiourea and enamine; And/or solidifying agent is selected from the 2-methyl isophthalic acid, the reaction product of 5-pentane diamine and mibk, 2-methyl isophthalic acid, the reaction product of 5-pentane diamine and pimelinketone, the reaction product of 2-methyl pentamethylene diamine and furfural, benzaldehyde and 2-methyl isophthalic acid, the reaction product of 5-pentane diamine; Furfural and 2-methyl isophthalic acid, the reaction product of 5-pentane diamine, the reaction product of benzaldehyde and diamino-ditan, the reaction product of furfural and diamino-ditane, thanomin mibk imines, hexamethylene diamine mibk diimine, diethylenetriamine mibk diamines enamine, N-(2-amino-ethyl)-piperazine ring hexanone imino--enamine, thanomin benzaldehyde imines, 2-(2-amino-ethyl)-thanomin furfural imines, the poly-imines of poly-aminophenyl methane mibk, the poly-imines of poly-aminophenyl-methane furfural, 1-octadecylamine benzaldehyde imines, fat-diamines furfural imines, piperazine MEK two-enamine, diethanolamine, the pimelinketone enamine, N-(2-hydroxyethyl) piperazine ring hexanone enamine, the acetyl benzophenone enamino diimine of piperazine-acetyl benzophenone two-enamine and diethylenetriamine.
A kind of method for preparing wood fibre or cellulosic substrate mixture, it comprises the steps:
(a) react the surface that system applies one of described substrate with liquid adhesive, described reaction system comprises:
(i) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0;
(ii) solidifying agent, it has at least 1 imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage in the described adhesive reaction system;
(b) described surface is faced toward the surperficial compressed together of second substrate;
(c) solidify described reaction system.
These class methods, wherein, described adhesive reaction system at room temperature solidifies; And/or to have 1 substrate material at least be wooden or papery.
Adopt this class methods prepared layer stampings.
This class laminated product, having 1 substrate at least is wooden or papery.
A kind of liquid adhesive/seal gum reaction system, it comprises:
(a) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0, wherein, described polymeric polyisocyanate is not to give polymeric isocyanate;
(b) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate group of polyisocyanate salt was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage.
In this class reaction system, polyisocyanate salt and solidifying agent at room temperature are liquid, and the number-average molecular weight of polymeric polyisocyanate is 100 to 5000; Polymeric polyisocyanate is a polyphenylene methane polymeric polyisocyanate; Polymeric polyisocyanate is that polyphenylene methane polymeric polyisocyanate and solidifying agent are aromatics imino-functional compounds; And/or solidifying agent is selected from the 2-methyl isophthalic acid, the reaction product of 5-pentane-diamines and mibk, the 2-methyl isophthalic acid, the reaction product of 5-pentane diamine and pimelinketone, the reaction product of 2-methyl pentamethylene diamine and furfural, benzaldehyde and 2-methyl isophthalic acid, the reaction product of 5-pentane diamine, furfural and 2-methyl isophthalic acid, the reaction product of 5-pentane diamine, the reaction product of benzaldehyde and diamino-ditan; Thanomin mibk imines, hexamethylene diamine mibk diimine, diethylenetriamine mibk diamines enamine, N-(2-amino-ethyl) piperazine ring hexanone imino-enamine, thanomin benzaldehyde imines, 2-(2-amino-ethyl)-thanomin furfural imines, the poly-imines of poly-aminophenyl-methane mibk, the poly-imines of poly-aminophenyl-methane furfural, 1-octadecylamine benzaldehyde imines and fat-diamines furfural imines, piperazine MEK two-enamine, diethanolamine pimelinketone enamine, (N-(2-hydroxyethyl) piperazine ring hexanone enamine, the acetyl benzophenone enamino diimine of piperazine-acetyl benzophenone two-enamine and diethylenetriamine.
A kind of method that two kinds of substrates are bonded together, it comprises the steps:
(a) react the surface that system applies one of described substrate with liquid adhesive, described reaction system comprises:
(i) polymeric polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0, wherein, described polymeric polyisocyanate is not to give polymeric isocyanate;
(ii) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the isocyanate groups of polymeric polyisocyanate was at least 2: 1 with the molecule number ratio of imino-or enamino functional linkage in the described reaction system;
(b) with described surface to seeing the surperficial compressed together of second substrate;
(c) solidify described reaction system
In these class methods, described adhesive reaction system at room temperature solidifies, at least one substrate be selected from that wood, paper, rice husk, cement, stone, cotton, grass, bract, sugarcane are clear, nutshell, polymeric film and polymer flake, polymer foams, metal and filamentary material; And/or at least one substrate material is made wooden or papery.
With these class methods prepared layer stampings.
This class laminated product, having a substrate at least is wooden or papery.
A kind of method that seals substrate surface, it comprises the steps:
(a) be applied to few substrate surface with liquid sealant reaction system, described reaction system comprises:
(i) polyisocyanate, isocyanate groups and number averaged isocyanate functionality that it has the aromatics connection are 1.8 to 4.0, wherein, described polymeric polyisocyanate is not to give polymeric isocyanate;
(ii) solidifying agent, it has at least one imino-or enamino functional linkage, and wherein, the molecule number of the isocyanate groups of polymeric polyisocyanate and inferior nitrogen base or enamino functional linkage is than at least 2: 1 in the described seal gum reaction system;
(b) solidify described seal gum reaction system.
With the claim is benchmark, has represented protection scope of the present invention.
Claims (5)
1. method for preparing mixture wood fibre or cellulosic substrate, this method comprises the steps:
(a) react the surface that system applies one of described lignocellulose or cellulosic substrate with liquid adhesive, described reaction system comprises:
(i) isocyanate groups and its number averaged isocyanate functionality that a kind of polymeric polyisocyanate, this polymeric polyisocyanate have the aromatics connection are 1.8 to 4.0;
(ii) a kind of solidifying agent, this solidifying agent have at least 1 imino-or enamino functional linkage, wherein, in the reaction system sum and the imino-or the enamino functional linkage of the isocyanate groups of polymeric polyisocyanate the molecule number ratio of sum be 3: 1 to 10: 1.
(b) described surface is faced toward the surperficial compressed together of second substrate;
(c) solidify described reaction system.
2. according to the process of claim 1 wherein that this conglutination reaction system is in self-vulcanizing.
3. according to the process of claim 1 wherein that at least a substrate material is wood or paper.
4. one kind by the prepared lamination object of the method for claim 1.
5. according to the lamination object of claim 4, wherein at least a substrate material is wood or paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919117068A GB9117068D0 (en) | 1991-08-08 | 1991-08-08 | Cold curable polyisocyanate adhesive and sealant systems |
| GB9117068.8 | 1991-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1069282A CN1069282A (en) | 1993-02-24 |
| CN1056867C true CN1056867C (en) | 2000-09-27 |
Family
ID=10699654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92109227A Expired - Fee Related CN1056867C (en) | 1991-08-08 | 1992-08-07 | Polyisocyanate adhesive and sealant systems |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5981683A (en) |
| EP (1) | EP0527568B1 (en) |
| JP (1) | JPH05247430A (en) |
| KR (1) | KR100248849B1 (en) |
| CN (1) | CN1056867C (en) |
| AU (1) | AU655293B2 (en) |
| CA (1) | CA2075457A1 (en) |
| DE (1) | DE69213613T2 (en) |
| ES (1) | ES2091412T3 (en) |
| GB (1) | GB9117068D0 (en) |
| HK (1) | HK1001689A1 (en) |
| ZA (1) | ZA925561B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109415478A (en) * | 2016-05-10 | 2019-03-01 | 陶氏环球技术有限责任公司 | Two-component solventless adhesive composition comprising amine-initiated polyol |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368714B1 (en) | 1993-10-14 | 2002-04-09 | John Russell Robertson | Moisture-activated adhesive compositions |
| US5554438A (en) * | 1994-07-22 | 1996-09-10 | Imperial Chemical Industries, Plc | Self-release binder system |
| WO1997001529A1 (en) * | 1995-06-28 | 1997-01-16 | Minnesota Mining And Manufacturing Company | Ketimine curing agents and rapidly curing magnetic recording media and films prepared with ketimines |
| CA2360100A1 (en) * | 1999-01-27 | 2000-08-03 | Huntsman International Llc | Moisture-activated adhesive compositions |
| US6855765B2 (en) * | 2001-12-12 | 2005-02-15 | National University Of Singapore | Heat and hot water resistant polyurethane sealant |
| US20040170856A1 (en) * | 2002-12-04 | 2004-09-02 | Bill Arndell | Laminated wood products and process for making the same |
| US20050085596A1 (en) * | 2003-10-17 | 2005-04-21 | The Yokohama Rubber Co., Ltd. | Curable resin composition |
| US7572461B2 (en) | 2004-03-05 | 2009-08-11 | Kenneth I. Sawyer | Borer-resistant wood, wood products, and wooden structures and methods |
| US20090068479A1 (en) * | 2007-09-11 | 2009-03-12 | Sika Technology Ag | Moisture-reactive adhesive compositions with very low temperature dependency of the shear modulus |
| EP2036931A1 (en) * | 2007-09-11 | 2009-03-18 | Sika Technology AG | Moisture curable adhesive compositions with low temperature-dependence of the shear module |
| CN103214787B (en) * | 2013-05-07 | 2014-12-10 | 黑龙江省木材科学研究所 | Resorcinol modified phenolic resin composite curing agent and preparation method thereof |
| TWI793073B (en) * | 2016-05-10 | 2023-02-21 | 美商陶氏全球科技有限責任公司 | Two-component solventless adhesive compositions comprising an amine-initiated polyol |
| CN108138022A (en) | 2016-09-29 | 2018-06-08 | Dic株式会社 | Bonding agent, stacked film and bonding agent glycol composition using it |
| TWI627250B (en) * | 2017-01-04 | 2018-06-21 | 台虹科技股份有限公司 | Adhesive composition and application thereof |
| CN110240794A (en) * | 2019-05-06 | 2019-09-17 | 阜阳大可新材料股份有限公司 | A kind of mould proof fiber board adhesive |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853454A (en) * | 1986-07-23 | 1989-08-01 | Basf Aktiengesellschaft | Preparation of storage-stable, moisture-cured, single-component polyurethane systems and their uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE674368A (en) * | 1964-12-28 | |||
| DE2116882C3 (en) * | 1971-04-06 | 1985-05-15 | Schering AG, 1000 Berlin und 4709 Bergkamen | Enamine compounds and their preparation |
| DE2651479C2 (en) * | 1976-11-11 | 1986-03-20 | Schering AG, 1000 Berlin und 4709 Bergkamen | Elastic adhesive |
| US4507443A (en) * | 1984-02-23 | 1985-03-26 | The B. F. Goodrich Company | Sealant and coating composition |
| DE3607996A1 (en) * | 1986-03-11 | 1987-09-17 | Basf Ag | MOISTURE-HARDENING, STORAGE-STABLE, 1-COMPONENT POLYURETHANE SYSTEMS AND THEIR USE |
| US4935460A (en) * | 1987-03-11 | 1990-06-19 | Ici Americas Inc. | Reaction injection molding compositions |
| GB8705801D0 (en) * | 1987-03-11 | 1987-04-15 | Ici Plc | Injection moulding compositions |
| EP0375318A3 (en) * | 1988-12-21 | 1991-01-23 | MITSUI TOATSU CHEMICALS, Inc. | Polyaldimine derivatives |
| US5087661A (en) * | 1990-07-20 | 1992-02-11 | Mitsui Toatsu Chemicals, Inc. | Moisture curable polyurethane composition comprising polyaldimine |
-
1991
- 1991-08-08 GB GB919117068A patent/GB9117068D0/en active Pending
-
1992
- 1992-07-20 AU AU20393/92A patent/AU655293B2/en not_active Ceased
- 1992-07-23 ZA ZA925561A patent/ZA925561B/en unknown
- 1992-07-24 EP EP92306786A patent/EP0527568B1/en not_active Expired - Lifetime
- 1992-07-24 DE DE69213613T patent/DE69213613T2/en not_active Expired - Fee Related
- 1992-07-24 ES ES92306786T patent/ES2091412T3/en not_active Expired - Lifetime
- 1992-08-04 JP JP4208112A patent/JPH05247430A/en active Pending
- 1992-08-04 US US07/925,347 patent/US5981683A/en not_active Expired - Fee Related
- 1992-08-06 CA CA002075457A patent/CA2075457A1/en not_active Abandoned
- 1992-08-07 CN CN92109227A patent/CN1056867C/en not_active Expired - Fee Related
- 1992-08-07 KR KR1019920014167A patent/KR100248849B1/en not_active Expired - Fee Related
-
1998
- 1998-01-21 HK HK98100541A patent/HK1001689A1/en not_active IP Right Cessation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853454A (en) * | 1986-07-23 | 1989-08-01 | Basf Aktiengesellschaft | Preparation of storage-stable, moisture-cured, single-component polyurethane systems and their uses |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109415478A (en) * | 2016-05-10 | 2019-03-01 | 陶氏环球技术有限责任公司 | Two-component solventless adhesive composition comprising amine-initiated polyol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1069282A (en) | 1993-02-24 |
| EP0527568B1 (en) | 1996-09-11 |
| GB9117068D0 (en) | 1991-09-25 |
| KR100248849B1 (en) | 2000-03-15 |
| JPH05247430A (en) | 1993-09-24 |
| CA2075457A1 (en) | 1993-02-09 |
| DE69213613D1 (en) | 1996-10-17 |
| HK1001689A1 (en) | 1998-07-03 |
| ZA925561B (en) | 1993-05-03 |
| AU2039392A (en) | 1993-02-11 |
| DE69213613T2 (en) | 1997-02-20 |
| ES2091412T3 (en) | 1996-11-01 |
| US5981683A (en) | 1999-11-09 |
| KR930004426A (en) | 1993-03-22 |
| EP0527568A3 (en) | 1993-03-31 |
| AU655293B2 (en) | 1994-12-15 |
| EP0527568A2 (en) | 1993-02-17 |
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